High temperature atomic layer deposition of silicon oxide thin films

ABSTRACT

Atomic layer deposition (ALD) process formation of silicon oxide with temperature&gt;500° C. is disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This patent application is a divisional application of U.S. Ser. No.15/248,214, filed on Aug. 26, 2016, which, in turn, is a continuationapplication of U.S. Ser. No. 13/857,507, filed on Apr. 5, 2013, which,in turn, claims the benefit of priority under 35 U.S.C. § 119(e) of U.S.provisional patent application Ser. No. 61/623,217, filed on Apr. 12,2012, the disclosures of which are incorporated herein by reference intheir entirety.

BACKGROUND OF THE INVENTION

Described herein is a composition and method for the formation of asilicon oxide film. More specifically, described herein is a compositionand method for formation of a silicon oxide film at one or moredeposition temperatures of about 500° C. or greater and using an atomiclayer deposition (ALD) process.

Thermal oxidation is a process commonly used to deposit high purity andhighly conformal silicon oxide films such as silicon dioxide (SiO₂) insemiconductor applications. However, the thermal oxidation process has avery low deposition rate, e.g., than 0.03 Å/s at 700° C. which makes itimpractical for high volume manufacturing processes (see, for example,Wolf, S., “Silicon Processing for the VLSI Era Vol. 1—ProcessTechnology”, Lattice Press, C A, 1986).

Atomic Layer Deposition (ALD) and Plasma Enhanced Atomic LayerDeposition (PEALD) are processes used to deposit silicon dioxide (SiO₂)conformal film at low temperature (<500° C.). In both ALD and PEALDprocesses, the precursor and reactive gas (such as oxygen or ozone) areseparately pulsed in certain number of cycles to form a monolayer ofsilicon dioxide (SiO₂) at each cycle. However, silicon dioxide (SiO₂)deposited at low temperatures using these processes may contain levelsof impurities such as carbon (C), nitrogen (N), or both which aredetrimental to semiconductor applications. To remedy this, one possiblesolution would be to increase deposition temperature such as 500° C. orgreater. However, at these higher temperatures, conventional precursorsemployed by semi-conductor industries tend to self-react, thermallydecompose, and deposit in CVD mode rather than ALD mode. The CVD modedeposition has reduced conformality compared to ALD deposition,especially in high aspect ratio structure in semiconductor applications.In addition, the CVD mode deposition has less control of film ormaterial thickness than the ALD mode deposition.

JP2010275602 and JP2010225663 disclose the use of a raw material to forma Si containing thin film such as, silicon oxide by a chemical vapordeposition (CVD) process at a temperature range of from 300-500° C. Theraw material is an organic silicon compound, represented by formula: (a)HSi(CH₃)(R¹)(NR²R³), wherein, R¹ represents NR⁴R⁵ or a 1C-5C alkylgroup; R² and R⁴ each represent a 1C-5C alkyl group or hydrogen atom;and R³ and R⁵ each represent a 1C-5C alkyl group); or (b)HSiCl(NR¹R²)(NR³R⁴), wherein R¹ and R³ independently represent an alkylgroup having 1 to 4 carbon atoms, or a hydrogen atom; and R² and R⁴independently represent an alkyl group having 1 to 4 carbon atoms. Theorganic silicon compounds contained H—Si bonds

U.S. Pat. No. 7,084,076 (“the '076 patent”) discloses a halogenatedsiloxane such as hexachlorodisiloxane (HCDSO) that is used inconjunction with pyridine as a catalyst for ALD deposition below 500° C.to form silicon dioxide.

U.S. Pat. No. 6,992,019 (“the '019 patent”) discloses a method forcatalyst-assisted atomic layer deposition (ALD) to form a silicondioxide layer having superior properties on a semiconductor substrate byusing a first reactant component consisting of a silicon compound havingat least two silicon atoms, or using a tertiary aliphatic amine as thecatalyst component, or both in combination, together with relatedpurging methods and sequencing. The precursor used ishexachlorodisilane. The deposition temperature is between 25-150° C.

Thus, there is a need to develop a process for forming a high quality,low impurity, high conformal silicon oxide film using an atomic layerdeposition (ALD) process or an ALD-like process, such as withoutlimitation a cyclic chemical vapor deposition process, to replacethermal-based deposition processes. Further, it may be desirable todevelop a high temperature deposition (e.g., deposition at one or moretemperatures of 500° C.) to improve one or more film properties, such aspurity and/or density, in an ALD or ALD-like process.

BRIEF SUMMARY OF THE INVENTION

Described herein is a process for the deposition of a silicon oxidematerial or film at high temperatures, e.g., at one or more temperaturesof 500° C. or greater, in an atomic layer deposition (ALD) or anALD-like process.

One embodiment provides a process to deposit a silicon oxide film onto asubstrated comprises steps of: a. providing a substrate in a reactor; b.introducing into the reactor at least one silicon precursor; c. purgingthe reactor with purge gas; d. introducing an oxygen source into thereactor; and e. purging the reactor with purge gas; and wherein steps bthrough e are repeated until a desired thickness of silicon oxide isdeposited, wherein the process in conducted at one or more temperaturesranging from 500 to 800° C. and one or more pressures ranging from 50miliTorr (mT) to 760 Torr, and wherein the at least one siliconprecursor having a formula selected from the group consisting ofmethoxytrimethylsilane, ethoxytrimethylsilane,iso-propoxytrimethylsilane, tert-butoxytrimethylsilane,tert-pentoxytrimethylsilane, phenoxytrimethylsilane,acetoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane,iso-propoxytriethylsilane, tert-butoxytriethylsilane,tert-pentoxytriethylsilane, phenoxytriethylsilane,acetoxytriethylsilane, methoxydimethylsilane, ethoxydimethylsilane,iso-propoxydimethylsilane, tert-butoxydimethylsilane,tert-pentoxydimethylsilane, phenoxydimethylsilane,acetoxydimethylsilane, methoxydimethylphenylsilane,ethoxydimethyiphenylsilane, iso-propoxydimethylphenylsilane,tert-butoxydimethylphenylsilane, tert-pentoxydimethylphenylsilane,phenoxydimethylphenylsilane, acetoxydimethylphenylsilane,dimethoxydimethylsilane, diethoxydimethylsilane,di-isopropoxydimethylsilane, di-t-butoxydimethylsilane,diacytoxydimethylsilane, dimethoxydiethylsilane, diethoxydiethylsilane,di-isopropoxydiethylsilane, di-t-butoxydiethylsilane,diacytoxydiethylsilane, dimethoxydi-isopropylsilane,diethoxydi-isopropylsilane, di-isopropoxydi-isopropylsilane,di-t-butoxydi-isopropylsilane, diacytoxydi-isopropylsilane,dimethoxymethylvinylsilane, diethoxymethylvinylsilane,di-isopropoxymethylvinylsilane, di-t-butoxymethylvinylsilane,diacytoxymethylvinylsilane,1,1,3,4-tetramethyl-1-sila-2,5-dioxacyclopentane,1,1,3,3,4,4-hexamethyl-1-sila-2,5-dioxacyclopentane, and mixturesthereof.

Another embodiment provides a process to deposit a silicon oxide filmonto a substrated comprises steps of: a. providing a substrate in areactor; b. introducing into the reactor at least one silicon precursor;c. purging the reactor with purge gas; d. introducing an oxygen sourceinto the reactor; and e. purging the reactor with purge gas; and whereinsteps b through e are repeated until a desired thickness of siliconoxide is deposited, wherein the process in conducted at one or moretemperatures ranging from 500 to 800° C. and one or more pressuresranging from 50 miliTorr (mT) to 760 Torr, wherein the at least onesilicon precursor having a formula selected from the group consisting of1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3,3-hexaethyldisilazane,1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane,1,1,1,2,3,3,3-heptamethyldisilazane,1,1,1,3,3,3-hexaethyl-2-methyldisilazane,1,1,2,3,3-pentamethyldisilazane, 1,1,3,3-tetraethyl-2-methyldisilazane,1,1,1,3,3,3-hexamethyl-2-ethyldisilazane,1,1,1,2,3,3,3-heptaethyldisilazane,1,1,3,3-tetramethyl-2-ethyldisilazane, 1,1,2,3,3-pentaethyldisilazane,1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane,1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane,1,1,3,3-tetramethyl-2-isopropyldisilazane,1,1,3,3-tetraethyl-2-isopropyldisilazane, and mixtures thereof.

In one or more embodiments described above, the purge gas is selectedfrom the group consisting of nitrogen, helium and argon.

In one or more embodiments described above, the oxygen source isselected from the group consisting of oxygen, oxygen plasma, watervapor, water vapor plasma, hydrogen peroxide, nitrous oxide, and ozoneand combination thereof.

BRIEF DESCRIPTION OF SEVERAL VIEWS OF THE DRAWINGS

FIG. 1 shows the deposition rate of dimethylaminotrimethylsilane(DMATMS) and diethylaminotrimethylsilane (DEAMTS) as function oftemperatures, suggesting both precursors can have an ALD window up to650° C.

FIG. 2 provides a mass spectrum of2,6-dimethylpiperidinotrimethylsilane.

FIG. 3 provides current vs. electric field for SiO₂ films deposited at650° C. with DMATMS vs. thermal oxide.

DETAILED DESCRIPTION OF THE INVENTION

Described herein are compositions and processes related to the formationof a silicon oxide containing film, such as a silicon oxynitride film, astoichiometric or non-stoichiometric silicon oxide film, a silicon oxidefilm or combinations, thereof with one or more temperatures, of 500° C.or greater, in an atomic layer deposition (ALD) or in an ALD-likeprocess, such as without limitation a cyclic chemical vapor depositionprocess (CCVD).

Typical ALD processes in the prior art uses an oxygen source, oroxidizer such as oxygen, oxygen plasma, water vapor, water vapor plasma,hydrogen peroxide, or ozone source directly to form SiO₂ at processtemperatures ranging from 25 to 500° C. The deposition steps comprisesof:

a. providing a substrate in a reactor

b. introducing into the reactor a silicon precursor

c. purging reactor with purge gas

d. introducing oxygen source into the reactor; and

e. purging reactor with purge gas.

In the prior art process, steps b through e are repeated until desiredthickness of film is deposited

It is believed that high temperature process, above 500° C., may yieldbetter film quality in term of film purity and density. ALD processprovides good film step coverage. However, typical organosiliconprecursors used in ALD or PEALD only deposit films in ALD mode within acertain temperature range. When temperature is higher than this range,thermal decomposition of the precursor occurs which causes either gasphase reaction or continuous substrate surface reaction which changesthe deposition process to CVD mode, rather than the desired ALD mode.

Not being bound by theory, for ALD or ALD-like deposition process at oneor more temperatures greater than 500° C., the silicon precursormolecules described herein should have at least one anchoringfunctionality, which reacts with certain reactive sites on the substratesurface to anchor a monolayer of silicon species. The anchoringfunctionalities can be selected from a halide (Cl, Br, I) group, anamino group, or an alkoxy group, preferably an amino-group such asdimethylamino or diethylamino groups. The silicon precursor should alsohave a passive functionality in that it is chemically stable as toprevent further surface reaction, leading to a self-limiting process.The passivating functionality is selected from different alkyl groupssuch as methyl, ethyl, phenyl groups, preferably a methyl group. Theremaining groups on the surface can then be oxidized to form a Si—O—Silinkage as well as hydroxyl groups. In addition, hydroxyl sources suchas H₂O or water plasma can also be introduced into the reactor to formmore hydroxyl groups as reactive sites for the next ALD cycle asdemonstrated in the following Scheme 1.

In one embodiment, the at least one silicon precursor described hereinis a compound having the following formula I:R¹R² _(m)Si(NR³R⁴)_(n)X_(p)  I.wherein R¹, R², and R³ are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R⁴is selected from, a linear or branched C₁ to C₁₀ alkyl group, and a C₆to C₁₀ aryl group, a C₃ to C₁₀ alkylsilyl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide selected from the groupconsisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; and p is 0 to 2and m+n+p=3. Examples of precursors having Formula I include are but notlimited to: diethylaminotrimethylsilane, dimethylaminotrimethylsilane,ethylmethylaminotrimethylsilane, diethylaminotriethylsilane,dimethylaminotriethylsilane, ethylmethylaminotriethylsilane,t-butylaminotriethylsilane, iso-propylaminotriethylsilane,di-isopropylaminotriethylsilane, pyrrolidinotriethylsilane,t-butylaminotrimethylsilane, iso-propylaminotrimethylsilane,di-isopropylaminotrimethylsilane, pyrrolidinotrimethylsilane,diethylaminodimethylsilane, dimethylaminodimethylsilane,ethylmethylaminodimethylsilane, t-butylaminodimethylsilane,iso-propylaminodimethylsilane, di-isopropylaminodimethylsilane,pyrrolidinodimethylsilane, diethylaminodiethylsilane,dimethylaminodiethylsilane, ethylmethylaminodiethylsilane,t-butylaminodiethylsilane, iso-propylaminodiethylsilane,di-isopropylaminodiethylsilane, pyrrolidonodiethylsilane,bis(diethylamino)dimethylsilane, bis(dimethylamino)dimethylsilane,bis(ethylmethylamino)dimethylsilane,bis(di-isopropyllamino)dimethylsilane,bis(iso-propylamino)dimethylsilane, bis(tert-butylamino)dimethylsilane,dipyrrolidinodimethylsilane, bis(diethylamino)diethylsilane,bis(dimethylamino)diethylsilane, bis(ethylmethylamino)diethylsilane,bis(di-isopropyllamino)diethylsilane, bis(iso-propylamino)diethylsilane,bis(tert-butylamino)diethylsilane, dipyrrolidinodiethylsilane,bis(diethylamino)methylvinylsilane, bis(dimethylamino)methylvinylsilanebis(ethylmethylamino)methylvinylsilane,bis(di-isopropyllamino)methylvinylsilane,bis(iso-propylamino)methylvinylsilane,bis(tert-butylamino)methylvinylsilane, dipyrrolidinomethylvinylsilane,2,6-dimethylpiperidinomethylsilane,2,6-dimethylpiperidinodimethylsilane,2,6-dimethylpiperidinotrimethylsilane, tris(dimethylamino)phenylsilane,tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, andtris(dimethylamino)chlorosilane.

Further examples of Group I silicon precursors wherein R⁴ in Formula Iis a C₃ to C₁₀ alkylsilyl group include but are not limited to:1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3,3-hexaethyldisilazane,1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane,1,1,1,2,3,3,3-heptamethyldisilazane,1,1,1,3,3,3-hexaethyl-2-methyldisilazane,1,1,2,3,3-pentamethyldisilazane, 1,1,3,3-tetraethyl-2-methyldisilazane,1,1,1,3,3,3-hexamethyl-2-ethyldisilazane,1,1,1,2,3,3,3-heptaethyldisilazane,1,1,3,3-tetramethyl-2-ethyldisilazane, 1,1,2,3,3-pentaethyldisilazane,1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane,1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane,1,1,3,3-tetramethyl-2-isopropyldisilazane, and1,1,3,3-tetraethyl-2-isopropyldisilazane.

In a further embodiment, the at least one silicon precursor describedherein is a compound having the following Formula II:R¹R² _(m)Si(OR³)_(n)(OR⁴)_(q)X_(p)  II.wherein R¹ and R² are each independently selected from hydrogen, alinear or branched C₁ to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group; R³and R⁴ are each independently selected from a linear or branched C₁ toC₁₀ alkyl group, and a C₆ to C₁₀ aryl group; wherein R³ and R⁴ arelinked to form a cyclic ring structure or R³ and R⁴ are not linked toform a cyclic ring structure; X is a halide atom selected from the groupconsisting of Cl, Br and I; m is 0 to 3; n is 0 to 2; q is 0 to 2 and pis 0 to 2 and m+n+q+p=3. Examples of such Group II silicon precursorsinclude but are not limited to: methoxytrimethylsilane,ethoxytrimethylsilane, iso-propoxytrimethylsilane,tert-butoxytrimethylsilane, tert-pentoxytrimethylsilane,phenoxytrimethylsilane, acetoxytrimethylsilane, methoxytriethylsilane,ethoxytriethylsilane, iso-propoxytriethylsilane,tert-butoxytriethylsilane, tert-pentoxytriethylsilane,phenoxytriethylsilane, acetoxytriethylsilane, methoxydimethylsilane,ethoxydimethylsilane, iso-propoxydimethylsilane,tert-butoxydimethylsilane, tert-pentoxydimethylsilane,phenoxydimethylsilane, acetoxydimethylsilane,methoxydimethylphenylsilane, ethoxydimethylphenylsilane,iso-propoxydimethylphenylsilane, tert-butoxydimethylphenylsilane,tert-pentoxydimethylphenylsilane, phenoxydimethylphenylsilane,acetoxydimethylphenylsilane, dimethoxydimethylsilane,diethoxydimethylsilane, di-isopropoxydimethylsilane,di-t-butoxydimethylsilane, diacytoxydimethylsilane,dimethoxydiethylsilane, diethoxydiethylsilane,di-isopropoxydiethylsilane, di-t-butoxydiethylsilane,diacytoxydiethylsilane, dimethoxydi-isopropylsilane,diethoxydi-isopropylsilane, di-isopropoxydi-isopropylsilane,di-t-butoxydi-isopropylsilane, diacytoxydi-isopropylsilane,dimethoxymethylvinylsilane, diethoxymethylvinylsilane,di-isopropoxymethylvinylsilane, di-t-butoxymethylvinylsilane,diacytoxymethylvinylsilane,1,1,3,4-tetramethyl-1-sila-2,5-dioxacyclopentane, and1,1,3,3,4,4-hexamethyl-1-sila-2,5-dioxacyclopentane.

In the formulas above and throughout the description, the term “alkyl”denotes a linear or branched functional group having from 1 to 10, 3 to10, or 1 to 6 carbon atoms. Exemplary linear alkyl groups include, butare not limited to, methyl, ethyl, propyl, butyl, pentyl, and hexylgroups. Exemplary branched alkyl groups include, but are not limited to,isopropyl, isobutyl, sec-butyl, tert-butyl, iso-pentyl, tert-pentyl,isohexyl, and neohexyl. In certain embodiments, the alkyl group may haveone or more functional groups such as, but not limited to, an alkoxygroup, a dialkylamino group or combinations thereof, attached thereto.In other embodiments, the alkyl group does not have one or morefunctional groups attached thereto. The alkyl group may be saturated or,alternatively, unsaturated.

In the formulas above and throughout the description, the term “aryl”denotes an aromatic cyclic functional group having from 3 to 10 carbonatoms, from 5 to 10 carbon atoms, or from 6 to 10 carbon atoms.Exemplary aryl groups include, but are not limited to, phenyl, benzyl,chlorobenzyl, tolyl, and o-xylyl.

In the formulas above and throughout the description, the term “alkoxy”denotes an alkyl group which is linked to an oxygen atom (e.g., R—O) andmay have from 1 to 12 or from 1 to 6 carbon atoms. Exemplary alkoxygroups include, but are not limited to, methoxy, ethoxy, propoxy,isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentoxy,tert-pentoxy, isopentoxy, neo-pentoxy, hexoxy, and 2-ethylhexoxy. In theformulas above and throughout the description, the term “amino” denotesan alkyl or aromatic group which is linked to a nitrogen atom (e.g.,NR³R⁴ defined as above) and may have from 1 to 12 or from 1 to 6 carbonatoms. Exemplary amino groups include, but are not limited to,dimethylamino, diethylamino, tert-butylamino, cyclohexylamino,piperidino, alkyl substituted piperidino (for example2,6-dimethylpiperdino), pyrrolidino, alkyl substituted pyrrolidino (forexample 2,5-dimethylpyrrolidino), pyrrolyl, alkyl-substituted pyrrolyl,imidazolyl, and alkyl substituted imidazolyl groups.

In the formulas above and through the description, the term“unsaturated” as used herein means that the functional group,substituent, ring or bridge has one or more carbon double or triplebonds. An example of an unsaturated ring can be, without limitation, anaromatic ring such as a phenyl ring. The term “saturated” means that thefunctional group, substituent, ring or bridge does not have one or moredouble or triple bonds.

In the formulas above and throughout the description, the term“alkylsilyl” denotes a linear or branched functional group having from 3to 10. Exemplary alkylsilyl groups include, but are not limited to,trimethylsilyl, triethylsilyl, dimethylsilyl, diethylsilyl, anddimethylethylsilyl.

In certain embodiments, substituents R³ and R⁴ in Formula I or FormulaII can be linked together to form a ring structure. As the skilledperson will understand, where R³ and R⁴ are linked together to form aring R³ will include a bond for linking to R⁴ and vice versa. In theseembodiments, the ring structure can be unsaturated such as, for example,a cyclic alkyl ring, or saturated, for example, an aryl ring. Further,in these embodiments, the ring structure can also be substituted orsubstituted. Exemplary cyclic ring groups include, but not limited to,pyrrolidino, piperidino, and 2,6-dimethylpiperidino groups. In otherembodiments, however, substituent R³ and R⁴ are not linked.

In certain embodiments, the silicon films deposited using the methodsdescribed herein are formed in the presence of oxygen using an oxygensource, reagent or precursor comprising oxygen. An oxygen source may beintroduced into the reactor in the form of at least one oxygen sourceand/or may be present incidentally in the other precursors used in thedeposition process. Suitable oxygen source gases may include, forexample, water (H₂O) (e.g., deionized water, purifier water, and/ordistilled water), oxygen (O₂), oxygen plasma, ozone (O₃), N₂O, NO₂,carbon monoxide (CO), carbon dioxide (CO₂) and combinations thereof. Incertain embodiments, the oxygen source comprises an oxygen source gasthat is introduced into the reactor at a flow rate ranging from about 1to about 2000 standard cubic centimeters (sccm) or from about 1 to about1000 sccm. The oxygen source can be introduced for a time that rangesfrom about 0.1 to about 100 seconds. In one particular embodiment, theoxygen source comprises water having a temperature of 10° C. or greater.In embodiments wherein the film is deposited by an ALD or a cyclic CVDprocess, the precursor pulse can have a pulse duration that is greaterthan 0.01 seconds, and the oxygen source can have a pulse duration thatis less than 0.01 seconds, while the water pulse duration can have apulse duration that is less than 0.01 seconds. In yet anotherembodiment, the purge duration between the pulses that can be as low as0 seconds or is continuously pulsed without a purge in-between. Theoxygen source or reagent is provided in a molecular amount less than a1:1 ratio to the silicon precursor, so that at least some carbon isretained in the as deposited dielectric film.

In certain embodiments, the silicon oxide films further comprisesnitrogen. In these embodiments, the films are deposited using themethods described herein and formed in the presence ofnitrogen-containing source. A nitrogen-containing source may beintroduced into the reactor in the form of at least one nitrogen sourceand/or may be present incidentally in the other precursors used in thedeposition process. Suitable nitrogen-containing source gases mayinclude, for example, ammonia, hydrazine, monoalkylhydrazine,dialkylhydrazine, nitrogen, nitrogen/hydrogen, ammonia plasma, nitrogenplasma, nitrogen/hydrogen plasma, and mixture thereof. In certainembodiments, the nitrogen-containing source comprises an ammonia plasmaor hydrogen/nitrogen plasma source gas that is introduced into thereactor at a flow rate ranging from about 1 to about 2000 square cubiccentimeters (sccm) or from about 1 to about 1000 sccm. Thenitrogen-containing source can be introduced for a time that ranges fromabout 0.1 to about 100 seconds. In embodiments wherein the film isdeposited by an ALD or a cyclic CVD process, the precursor pulse canhave a pulse duration that is greater than 0.01 seconds, and thenitrogen-containing source can have a pulse duration that is less than0.01 seconds, while the water pulse duration can have a pulse durationthat is less than 0.01 seconds. In yet another embodiment, the purgeduration between the pulses that can be as low as 0 seconds or iscontinuously pulsed without a purge in-between.

The deposition methods disclosed herein may involve one or more purgegases. The purge gas, which is used to purge away unconsumed reactantsand/or reaction byproducts, is an inert gas that does not react with theprecursors. Exemplary purge gases include, but are not limited to, argon(Ar), nitrogen (N₂), helium (He), neon, hydrogen (H₂), and mixturesthereof. In certain embodiments, a purge gas such as Ar is supplied intothe reactor at a flow rate ranging from about 10 to about 2000 sccm forabout 0.1 to 1000 seconds, thereby purging the unreacted material andany byproduct that may remain in the reactor.

The respective step of supplying the precursors, oxygen source, thenitrogen-containing source, and/or other precursors, source gases,and/or reagents may be performed by changing the time for supplying themto change the stoichiometric composition of the resulting dielectricfilm.

Energy is applied to the at least one of the silicon precursor, oxygencontaining source, or combination thereof to induce reaction and to formthe dielectric film or coating on the substrate. Such energy can beprovided by, but not limited to, thermal, plasma, pulsed plasma, heliconplasma, high density plasma, inductively coupled plasma, X-ray, e-beam,photon, remote plasma methods, and combinations thereof. In certainembodiments, a secondary RF frequency source can be used to modify theplasma characteristics at the substrate surface. In embodiments whereinthe deposition involves plasma, the plasma-generated process maycomprise a direct plasma-generated process in which plasma is directlygenerated in the reactor, or alternatively a remote plasma-generatedprocess in which plasma is generated outside of the reactor and suppliedinto the reactor.

The at least one silicon precursors may be delivered to the reactionchamber such as a cyclic CVD or ALD reactor in a variety of ways. In oneembodiment, a liquid delivery system may be utilized. In an alternativeembodiment, a combined liquid delivery and flash vaporization processunit may be employed, such as, for example, the turbo vaporizermanufactured by MSP Corporation of Shoreview, Minn., to enable lowvolatility materials to be volumetrically delivered, which leads toreproducible transport and deposition without thermal decomposition ofthe precursor. In liquid delivery formulations, the precursors describedherein may be delivered in neat liquid form, or alternatively, may beemployed in solvent formulations or compositions comprising same. Thus,in certain embodiments the precursor formulations may include solventcomponent(s) of suitable character as may be desirable and advantageousin a given end use application to form a film on a substrate.

For those embodiments wherein the at least one silicon precursorprecursor(s) having Formula I or II is used in a composition comprisinga solvent and an at least one silicon precursor having Formula I or IIdescribed herein, the solvent or mixture thereof selected does not reactwith the silicon precursor. The amount of solvent by weight percentagein the composition ranges from 0.5% by weight to 99.5% or from 10% byweight to 75%. In this or other embodiments, the solvent has a boilingpoint (b.p.) similar to the b.p. of the at least one silicon precursorof Formula I or Formula II or the difference between the b.p. of thesolvent and the b.p. of the t least one silicon precursor of Formula Ior Formula II is 40° C. or less, 30° C. or less, or 20° C. or less, or10° C. or less. Alternatively, the difference between the boiling pointsranges from any one or more of the following end-points: 0, 10, 20, 30,or 40° C. Examples of suitable ranges of b.p. difference include withoutlimitation, 0 to 40° C., 20° to 30° C., or 10° to 30° C. Examples ofsuitable solvents in the compositions include, but are not limited to,an ether (such as 1,4-dioxane, dibutyl ether), a tertiary amine (such aspyridine, 1-methylpiperidine, 1-ethylpiperidine,N,N′-Dimethylpiperazine, N,N,N′,N′-Tetramethylethylenediamine), anitrile (such as benzonitrile), an alkane (such as octane, nonane,dodecane, ethylcyclohexane), an aromatic hydrocarbon (such as toluene,mesitylene), a tertiary aminoether (such as bis(2-dimethylaminoethyl)ether), or mixtures thereof.

As previously mentioned, the purity level of the at least one siliconprecursor of Formula I or Formula II is sufficiently high enough to beacceptable for reliable semiconductor manufacturing. In certainembodiments, the at least one silicon precursor of Formula I or FormulaII described herein comprise less than 2% by weight, or less than 1% byweight, or less than 0.5% by weight of one or more of the followingimpurities: free amines, free halides or halogen ions, and highermolecular weight species. Higher purity levels of the silicon precursordescribed herein can be obtained through one or more of the followingprocesses: purification, adsorption, and/or distillation.

In one embodiment of the method described herein, a cyclic depositionprocess such as ALD-like, ALD, or PEALD may be used wherein thedeposition is conducted using the at least one silicon precursor ofFormula I or Formula II and an oxygen source. The ALD-like process isdefined as a cyclic CVD process but still provides high conformalsilicon oxide films.

In certain embodiments, the gas lines connecting from the precursorcanisters to the reaction chamber are heated to one or more temperaturesdepending upon the process requirements and the container of the atleast one silicon precursor of Formula I or Formula II is kept at one ormore temperatures for bubbling. In other embodiments, a solutioncomprising the t least one silicon precursor of Formula I or Formula IIis injected into a vaporizer kept at one or more temperatures for directliquid injection.

A flow of argon and/or other gas may be employed as a carrier gas tohelp deliver the vapor of the at least one silicon precursor of FormulaI or Formula II to the reaction chamber during the precursor pulsing. Incertain embodiments, the reaction chamber process pressure is about 1Torr.

In a typical ALD or an ALD-like process such as a CCVD process, thesubstrate such as a silicon oxide substrate is heated on a heater stagein a reaction chamber that is exposed to the silicon precursor initiallyto allow the complex to chemically adsorb onto the surface of thesubstrate.

A purge gas such as argon purges away unabsorbed excess complex from theprocess chamber. After sufficient purging, an oxygen source may beintroduced into reaction chamber to react with the absorbed surfacefollowed by another gas purge to remove reaction by-products from thechamber. The process cycle can be repeated to achieve the desired filmthickness. In some cases, pumping can replace a purge with inert gas orboth can be employed to remove unreacted silicon precursors.

In this or other embodiments, it is understood that the steps of themethods described herein may be performed in a variety of orders, may beperformed sequentially, may be performed concurrently (e.g., during atleast a portion of another step), and any combination thereof. Therespective step of supplying the precursors and the oxygen source gasesmay be performed by varying the duration of the time for supplying themto change the stoichiometric composition of the resulting dielectricfilm.

One particular embodiment of the method described herein to deposit asilicon oxide film on a substrate comprises the following steps:

-   -   a. providing a substrate in a reactor    -   b. introducing into the reactor at least one silicon precursor        described herein having formula I, II, or both    -   c. purging the reactor with purge gas    -   d. introducing oxygen source into the reactor and    -   e. purging the reactor with purge gas        wherein steps b through e are repeated until a desired thickness        of the silicon oxide film is deposited.

In one particular embodiment of the method and composition describedherein, the silicon precursor is a compound having the following FormulaI:R¹R² _(m)Si(NR³R⁴)_(n)X_(p)  I.wherein R¹ is a methyl (Me) group, R² is a Me group, m=2, n=1, p=0, R³is selected from hydrogen, a linear or branched C₁ to C₁₀ alkyl group,and a C₆ to C₁₀ aryl group; R⁴ is selected from, a linear or branched C₁to C₁₀ alkyl group, and a C₆ to C₁₀ aryl group, a C₃ to C₁₀ alkylsilylgroup; wherein R³ and R⁴ are linked to form a cyclic ring structure orR³ and R⁴ are not linked to form a cyclic ring structure. Table 1 belowshows structures of exemplary silicon precursors having an anchoringfunctionality selected from a halide atom, an amine group, or an alkoxygroup and having a passivating functionally selected from an alkyl groupwhich is preferably a methyl or Me group. Not bound by theory, it isbelieved that the Si-Me groups are stable at temperatures higher than500° C. and provide a passivation functionality to prevent furthersurface reaction, leading to a self-limiting ALD or ALD-like process.

TABLE 1 Silicon precursors having at least one anchoring functionalityand at least one passivating functionality (e.g., 3 methyl groups).

Another embodiment of the method described herein introduces a hydroxylor OH source such as H₂O vapor after the oxidizing step. The goal inthis embodiment to repopulate the anchoring functionality or reactivesites for silicon precursor which anchor on the surface to form themonolayer. The deposition steps are comprised of:

a. providing a substrate in a reactor

b. introducing into the reactor one silicon precursor described above

c. purging reactor with purge gas

d. introducing oxidizer into the reactor

e. purging reactor with purge gas

f. introducing water vapor or hydroxyl source into the reactor; and

g. purging reactor with purge gas

wherein steps b through g are repeated until desired thickness isdeposited.

In an alternative embodiment of the method described herein, thedeposition steps are comprised of:

a. providing a substrate in a reactor

b. introducing into the reactor one silicon precursor described above

c. purging the reactor with purge gas

d. introducing oxygen source into the reactor

e. purging the reactor with purge gas

f. introducing water vapor or OH source into the reactor; and

g. purging the reactor with purge gas

wherein steps b through i are repeated until desired thickness isdeposited.

Yet another embodiment employs hydrogen peroxide or oxygen plasma toremove a passivating functionality or group such as methyl. Thedeposition steps are as follows:

a. providing a substrate in a reactor

b. introducing into the reactor one silicon precursor described above

c. purging reactor with purge gas

d. introducing ozone, hydrogen peroxide or oxygen plasma into thereactor; and

e. purging reactor with purge gas

wherein steps b through e are repeated until desired thickness isdeposited

Process temperature for the method described herein are one or moretemperatures ranging from 500° C. to 1000° C.; or 500° C. to 750° C.; or600° C. to 750° C.; or 600° C. to 800° C.

Deposition pressure ranges are one or more pressures ranging from 50miliTorr (mT) to 760 Torr, or from 500 mT-100 Torr. Purge gas can beselected from inert gas such as nitrogen, helium or argon. Oxidizer isselected from oxygen, peroxide, ozone or molecular oxygen from plasmaprocess.

EXAMPLES Example 1: Atomic Layer Deposition of Silicon Oxide Films withDimethylaminotrimethylsilane

Atomic layer deposition of silicon oxide films were conducted using thefollowing precursors: dimethylaminotrimethylsilane (DMATMS). Thedepositions were performed on a laboratory scale ALD processing tool.The silicon precursor was delivered to the chamber by vapor draw. Allgases (e.g., purge and reactant gas or precursor and oxygen source) werepreheated to 100° C. prior to entering the deposition zone. Gases andprecursor flow rates were controlled with ALD diaphragm valves with highspeed actuation. The substrates used in the deposition were 12 inch longsilicon strips. A thermocouple attached on the sample holder to confirmsubstrate temperature. Depositions were performed using ozone as oxygensource gas. Deposition parameters are provided in Table I.

TABLE I Process for Atomic Layer Deposition of Silicon Oxide Films withOzone Using DMATMS Step 1 6 sec Evacuate reactor <100 mT Step 2 VariableDose Silicon precursor Reactor pressure typically < 2 Torr Step 3 6 secPurge reactor with nitrogen Flow 1.5 slpm N₂ Step 4 6 sec Evacuatereactor <100 mT Step 5 4 sec Dose Ozone, 16-20% wt Step 6 6 sec Purgereactor with nitrogen Flow 1.5 slpm N₂

Steps 2 to 6 are repeated until a desired thickness is reached.Thickness and refractive indices of the films were measured using aFilmTek 2000SE ellipsometer by fitting the reflection data from the filmto a pre-set physical model (e.g., the Lorentz Oscillator model). Wetetch rate was performed using 1% solution of 49% hydrofluoric (HF) acidin deionized water. Thermal oxide wafers were used as reference for eachbatch to confirm solution concentration. Typical thermal oxide wafer wetetch rate for 1% HF in H₂O solution is 0.5 Å/s. Film thickness beforeand after etch was used to calculate wet etch rate. Carbon and nitrogenconcentration in the films were analyzed with Dynamic Secondary IonsMass Spectrometry (SIMS) technique. The % non-uniformity was calculatedfrom 6-point measurements using the following equation: %non-uniformity=((max−min)/(2*mean)). Film density was characterized withX-ray reflectometry (XRR). Table II summarizes SiO₂ films propertiesdeposited with a fixed dose (8 seconds) of the DMATMS precursor at awafer temperature ranging from 500 to 650° C.

TABLE II Silicon Oxide Film Properties Deposited with DMATMS C N WaferDeposition Non- concen- concen- temperature Rate uniformity WER tration(# of tration (# (Celcius) (Å/cycle) (%) (Å/s) atoms/cc) of atoms/cc)500 1.24 1.5 3.08 2.90E+19 1.68E+18 550 1.22 1.4 NA 3.82E+19 1.73E+18600 1.25 0.8 NA 3.49E+19 2.49E+18 650 1.32 1.0 2.07 2.25E+19 2.51E+18

Film densities for silicon oxides deposited from DMATMS ranged from 2.08to 2.23 g/cc.

FIG. 3 depicts the leakage current and breakdown comparison betweenthermal oxide and SiO₂ deposited with DMATMS at 650° C., demonstratingthat silicon oxide using DMATMS has electrical properties comparable tothermal oxide. Leakage current at 1-5 MV/cm, typical operating voltage,is within 1 order of magnitude of a thermal oxide typical deviceoperating voltage.

To confirm ALD mode deposition, multiple precursor doses were used priorto introducing ozone to ensure that the deposition is self-limiting.Deposition steps are listed below in Table III:

TABLE III ALD Conditions for Confirming ALD Mode Using DMATMS Step 1 6sec Evacuate reactor <100 mT Step 2a 2 sec Dose Silicon precursorReactor pressure typically < 2 Torr Step 2b 2 sec Evacuate reactor <100mT Step 3 6 sec Purge reactor with nitrogen Flow 1.5 slpm N₂ Step 4 6sec Evacuate reactor <100 mT Step 5 4 sec Dose Ozone, 16-20% weight Step6 6 sec Purge reactor with nitrogen Flow 1.5 slpm N₂

Steps 2a and 2b were repeated to introduce multiple doses of siliconprecursor. Both deposition rate and non-uniformity are reported in TableIV.

TABLE IV Deposition Rates and Film Non-Uniformities of SiO₂ filmsdeposited with multiple DMATMS doses Wafer DMATMS Deposition Non-temperature dose Rate uniformity (Celcius) (seconds) (Å/cycle) (%) 650 21.17 2.0 650 2 + 2 1.30 1.3 650 2 + 2 + 2 1.36 1.2

The deposition rates show self-limiting behavior and saturates withincreasing precursor doses which confirms ALD mode deposition at 650° C.

Example 2: Atomic Layer Deposition of Silicon Oxide Films withDiethylaminotrimethylsilane

Atomic layer deposition of silicon oxide films were conducteddiethylaminotrimethylsilane (DEATMS) using steps listed in Table I ofExample 1. Deposition rate and film non-uniformity of SiO₂ filmsdeposited with DEATMS at 500-650° C. at a fixed precursor dose (8seconds) are depicted in Table IV.

TABLE IV Deposition Rate and Film Non-Uniformity of SiO₂ films depositedwith fixed DEATMS dose Wafer Deposition Non- temperature Rate uniformity(Celcius) (Å/cycle) (%) 500 1.10 1.3 550 1.10 1.0 600 1.16 0.5 650 1.272.5

To confirm ALD mode deposition, multiple precursor doses were used priorto ozone deposition steps to ensure the deposition is self-limiting.Deposition steps are listed Table V below:

TABLE V ALD Conditions for Confirming ALD Mode Using DEATMS Step 1 6 secEvacuate reactor <100 mT Step 2a 2 sec Dose Silicon precursor Reactorpressure typically < 2 Torr Step 2b 2 sec Evacuate reactor <100 mT Step3 6 sec Purge reactor with nitrogen Flow 1.5 slpm N₂ Step 4 6 secEvacuate reactor <100 mT Step 5 4 sec Dose Ozone, 16-20% weight Step 6 6sec Purge reactor with nitrogen Flow 1.5 slpm N₂

Steps 2a and 2b are repeated to simulate multiple doses of siliconprecursor. Both deposition rate and non-uniformity are reported in TableVI.

TABLE VI Deposition Rate and Film Non-Uniformity of SiO₂ films depositedwith multiple DEATMS dose Wafer Precursor Deposition Non- temperaturedose Rate uniformity (Celcius) (seconds) (Å/cycle) (%) 650 2 1.01 2.3650 2 + 2 1.20 2.8 650 2 + 2 + 2 1.30 2.5 650 2 + 2 + 2 + 2 1.35 2.5

The deposition rates show self-limiting behavior and saturates withincreasing precursor doses which confirms ALD mode deposition at 650° C.

Example 3: Atomic Layer Deposition of Silicon Oxide Films on a PatternedSilicon Substrate with DMATMS

SiO₂ film was deposited on patterned silicon wafers with DMATMS. Thedeposition process was performed using ozone as the oxygen source gasand precursor double pulse of 8 seconds at 650° C. The film deposited onthe substrate was measured using field emission scanning electronmicroscopy (FESEM) Hitachi S-4800 SEM. The samples were mounted incross-sectional holders and examined using SEM operated at 2 kVaccelerating voltage. SiO₂ thickness measurements of samplecross-sections were taken at the top, the side wall, and the bottom ofthe trench. A review of the SEM cross-section of the SiO₂ film indicatedexcellent step coverage (>96%) and confirmed that the process is indeedan ALD process.

Example 4: Atomic Layer Deposition of Silicon Oxide Films withDiethylaminotriethylsilylane (DEATES)

Deposition of silicon oxide films were conducted using the siliconprecursor diethylaminotriethylsilane (DEATES) and ozone. The depositionsteps used are listed in Table I of Example 1. Table VII summarizesdeposition rates and non-uniformities of SiO₂ films deposited at wafertemperatures of 500 to 650° C. using DEATES.

TABLE VII Deposition Rates and Film Non-Uniformities of SiO₂ FilmsDeposited with Fixed DEATES Dose Wafer Deposition Non- temperature Rateuniformity (Celcius) (Å/cycle) (%) 500 0.91 1.44 550 0.97 1.1 600 1.187.8 650 2.53 24.8

Referring to Table VII, the deposition rates and film non-uniformitiesincreased at 600° C. which indicated some CVD reaction at 600° C. and afurther increase in CVD reaction at 650° C.

Example 5: Atomic Layer Deposition of Silicon Oxide Films withMethoxytrimethylsilylane

Atomic layers depositions of silicon oxide films were conducted usingthe silicon precursor methoxytrimethylsilylane. Depositions wereperformed using ozone at 650° C. with process steps listed in Table I ofExample 1. The substrate temperature was set at 650° C. The depositionrate was about 0.3 Å/cycle.

Example 6: Atomic Layer Deposition of Silicon Oxide Films withChlorotrimethylsilylane

Atomic layers deposition of silicon oxide films was conducted using thesilicon precursor chlorotrimethylsilylane. Depositions were performedusing ozone as the oxygen source gas and the process parameters of thedepositions are the same in Table I of Example 1. The substratetemperature was set at 650° C. The deposition rate was 0.5 Å/cycle.

Example 7: Atomic Layer Deposition of Silicon Oxide Films withHexamethyldisilazane

Atomic layers depositions of silicon oxide films were conducted usingthe silicon precursor hexamethyldisilane. Depositions were performedusing ozone at 650° C. with process steps listed in Table I ofExample 1. The deposition rate was about 1.3 Å/cycle.

Example 8: ALD Deposition of Silicon Oxide Film UsingBis(Dimethylamino)Dimethylsilane

Bisdimethylaminodimethylsilane (BDMADMS) was used as the siliconprecursor. BDMADMS has general structure of R¹R² _(m)Si(NR³R⁴)_(n),wherein R¹, R², R³, R⁴ are methyl, n=2, and m=1.

Depositions were performed on a laboratory scale ALD processing tool.Depositions were performed using ozone as the oxygen source gas and theprocess parameters of the depositions are the same in Table I.

Deposition rates and film non-uniformities of silicon oxide filmsdeposited using BDMADMS with fixed precursor dose (8 seconds) at500-650° C. are summarized in Table VIII:

TABLE VIII Deposition Rate and Film Non-Uniformity of SiO₂ filmsdeposited with fixed BDMADMS dose. Wafer Deposition Non- temperatureRate uniformity (Celcius) (Å/cycle) (%) 300 0.67 2.1 500 0.96 2.1 6501.72 5.0

Double precursor pulses process was used to further verify ALD mode.Table IX shows the deposition rate and non-uniformity of the films withsingle 8 sec pulse and double 8 second pulses.

TABLE IX Summary of Process Parameters and Results for BDMADMS WaferPrecursor Deposition Non- temperature Pulse Rate uniformity (Celcius)(seconds) (Å/cycle) (%) 650 8 1.72 5.0 650 8 + 8 2.05 7.8

As Table IX shows, the deposition rate increased significantly whendouble precursor pulses were used and the uniformity decreased, whichsuggested some CVD mode deposition.

Example 9: Synthesis of 2,6-dimethylpiperidinotrimethylsilane

In a 1000 ml three-necked round bottom flask equipped with an additionfunnel, a condenser, and a mechanical stirrer, 113 g (1.0 mol)2,6-dimethylpiperidine and 500 ml hexane were added. With stirring, 50.5g (0.5 mol) chlorotrimethylsilane was added dropwise through theaddition funnel. After the addition was completed, the reaction mixturewas refluxed for 6 hours. Cooling down to room temperature, the mixturewas filtered. The solid was washed with hexane, and the hexane solutionwas combined with the filtrate. Solvent hexane was removed bydistillation. 134 g 2,6-dimethylpiperidinotrimethylsilane was obtainedby fractional distillation. The yield was 75%. Mass spectrum provided inFIG. 2 confirmed that it is dimethylpiperidinotrimethylsilane withfragments at 185 (M), 170 (M-15).

The invention claimed is:
 1. A process to deposit a silicon oxide filmonto a substrate, comprising the steps of: a. providing a substrate in areactor; b. introducing into the reactor at least one silicon precursor;c. purging the reactor with purge gas; d. introducing an oxygen sourceinto the reactor; and e. purging the reactor with purge gas; and whereinsteps b through e are repeated until a desired thickness of siliconoxide is deposited, wherein the process in conducted at one or moretemperatures ranging from over 600 to 800° C. and one or more pressuresranging from 50 milliTorr (mT) to 760 Torr, wherein the at least onesilicon precursor having a formula selected from the group consisting ofmethoxytrimethylsilane, ethoxytrimethylsilane,iso-propoxytrimethylsilane, tert-butoxytrimethylsilane,tert-pentoxytrimethylsilane, phenoxytrimethylsilane,acetoxytrimethylsilane, methoxytriethylsilane, ethoxytriethylsilane,iso-propoxytriethylsilane, tert-butoxytriethylsilane,tert-pentoxytriethylsilane, phenoxytriethylsilane,acetoxytriethylsilane, methoxydimethylsilane, ethoxydimethylsilane,iso-propoxydimethylsilane, tert-butoxydimethylsilane,tert-pentoxydimethylsilane, phenoxydimethylsilane,acetoxydimethylsilane, methoxydimethylphenylsilane,ethoxydimethylphenylsilane, iso-propoxydimethylphenylsilane,tert-butoxydimethylphenylsilane, tert-pentoxydimethylphenylsilane,phenoxydimethylphenylsilane, acetoxydimethylphenylsilane,dimethoxydimethylsilane, diethoxydimethylsilane,di-isopropoxydimethylsilane, di-t-butoxydimethylsilane,diacytoxydimethylsilane, dimethoxydiethylsilane, diethoxydiethylsilane,di-isopropoxydiethylsilane, di-t-butoxydiethylsilane,diacytoxydiethylsilane, dimethoxydi-isopropylsilane,diethoxydi-isopropylsilane, di-isopropoxydi-isopropylsilane,di-t-butoxydi-isopropylsilane, diacytoxydi-isopropylsilane,dimethoxymethylvinylsilane, diethoxymethylvinylsilane,di-isopropoxymethylvinylsilane, di-t-butoxymethylvinylsilane,diacytoxymethylvinylsilane,1,1,3,4-tetramethyl-1-sila-2,5-dioxacyclopentane,1,1,3,3,4,4-hexamethyl-1-sila-2,5-dioxacyclopentane, and mixturesthereof.
 2. The process of claim 1, wherein the purge gas is selectedfrom the group consisting of nitrogen, helium and argon.
 3. The processof claim 1, wherein the oxygen source is selected from the groupconsisting of oxygen, peroxide, oxygen plasma, water vapor, water vaporplasma, hydrogen peroxide, and ozone source.
 4. The process of claim 1,further comprises steps f and g after step e: f. introducing water vaporor hydroxyl source into the reactor; and g. purging reactor with purgegas.
 5. A process to deposit a silicon oxide film onto a substrate,comprising the steps of: a. providing a substrate in a reactor; b.introducing into the reactor at least one silicon precursor; c. purgingthe reactor with purge gas; d. introducing an oxygen source into thereactor; and e. purging the reactor with purge gas; and wherein steps bthrough e are repeated until a desired thickness of silicon oxide isdeposited, wherein the process in conducted at one or more temperaturesranging from over 600 to 800° C. and one or more pressures ranging from50 milliTorr (mT) to 760 Torr, wherein the at least one siliconprecursor having a formula selected from the group consisting of1,1,1,3,3,3-hexamethyldisilazane, 1,1,1,3,3,3-hexaethyldisilazane,1,1,3,3-tetramethyldisilazane, 1,1,3,3-tetraethyldisilazane,1,1,1,2,3,3,3-heptamethyldisilazane,1,1,1,3,3,3-hexaethyl-2-methyldisilazane,1,1,2,3,3-pentamethyldisilazane, 1,1,3,3-tetraethyl-2-methyldisilazane,1,1,1,3,3,3-hexamethyl-2-ethyldisilazane,1,1,1,2,3,3,3-heptaethyldisilazane,1,1,3,3-tetramethyl-2-ethyldisilazane, 1,1,2,3,3-pentaethyldisilazane,1,1,1,3,3,3-hexamethyl-2-isopropyldisilazane, 1,1,1,3,3,3-hexaethyl-2-isopropyldisilazane,1,1,3,3-tetramethyl-2-isopropyldisilazane,1,1,3,3-tetraethyl-2-isopropyldisilazane, and mixtures thereof.
 6. Theprocess of claim 5, wherein the oxygen source is selected from the groupconsisting of oxygen, peroxide, oxygen plasma, nitrous oxide, watervapor, water vapor plasma, hydrogen peroxide, and ozone source.
 7. Theprocess of claim 5, wherein the process temperature ranges from 500° C.to 750° C.
 8. The process of claim 5, wherein the process temperatureranges from 600° C. to 750° C.
 9. The process of claim 5, wherein thepressure ranges from 50 milliTorr (mT) to 100 Torr.
 10. The process ofclaim 5, further comprises steps f and g after step e: f. introducingwater vapor or hydroxyl source into the reactor; and g. purging reactorwith purge gas.
 11. A film deposited by the process of claim
 1. 12. Afilm deposited by the process of claim 5.